JP6522900B2 - Nonionic water based urethane resin composition and paint containing the same - Google Patents

Description

  The present invention relates to a nonionic water-based polyurethane resin composition, and in particular, a nonionic water-based polyurethane resin composition having good storage stability under acidic conditions and excellent flexibility when used as a coating, and the resin composition A paint containing a substance.

  The water-based polyurethane resin composition can be used in various applications such as paints, adhesives, fiber sizing agents, synthetic leather, impregnating agents for substrates, backing materials, etc., but in particular, special clothing, automobiles, aircraft , Interiors of transportation vehicles such as buses and railway vehicles, furniture (chair, sofa, curtain, rattan etc.), building materials (in addition to housing, building materials for public facilities such as hotels, cinemas, public halls etc.), electronic circuit board materials etc. In the case of using it, high flame retardancy is required.

  Conventionally, halogen-based flame retardants have been used as flame retardants (for example, Patent Document 1), but in recent years non-halogenated flame retardants have been desired from the viewpoint of preventing environmental pollution, and phosphorus-based compounds Flame retardants have come to be used (for example, Patent Documents 2 and 3). However, since phosphorus compounds have lower flame retardance compared to halogen compounds, when using phosphorus compounds as a flame retardant, usually, the amount of resin used is almost equal to the amount of flame retardant used? Or, the amount of flame retardant used was increased. However, since the flame retardant generally tends to induce bleed out of the dye, there has been a drawback that the use of a large amount of the flame retardant tends to lower the color fastness.

The above disadvantages were ameliorated by polyurethane resin water dispersion (Patent Document 4) using a special urethane prepolymer and a special phosphorus compound, but in this case, the storage stability and coating under acidic conditions There is a disadvantage that the flexibility of the membrane is insufficient.
Then, as a result of repeating earnest research in order to solve the above-mentioned fault, the present inventors can obtain a good result, when a specific phosphoric acid ester compound is made to contain in nonionic water-based polyurethane resin composition. We found out what we can do and completed the present invention.

JP-A-9-250086 Japanese Patent Application Laid-Open No. 11-269766 JP 2000-126523 A WO 2014/045577

Therefore, the first object of the present invention is to provide a coating film which is excellent in flame retardancy despite the use of a small amount of phosphorus compound as a flame retardant and has good storage stability under acidic conditions. It is providing the water-based polyurethane resin composition which is excellent in the flexibility of the time.
A second object of the present invention is to provide a paint which is excellent in environmental compatibility, flame retardancy, storage stability under acidic conditions, and excellent in flexibility when used as a coating.

That is, the present invention comprises an isocyanate group-containing urethane prepolymer having a nonionic group , and at least one compound selected from phosphorus compounds represented by the following average composition formula (I): A nonionic water-based urethane resin composition, and a paint comprising the composition.

但し、上式中の、ｎは2.6〜１０の数、ｍは０又は１を表し、Ｒはそれぞれ独立に、水素原子、アルキル基又はフェニル基を表し、Ａは単結合、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−又は−Ｏ−を表す。
本発明における前記ノニオン性基を有するイソシアネート基含有ウレタンプレポリマーはポリエチレンオキサイド鎖を有することが好ましく、特に、高分子ポリオール及びポリオキシエチレン基を含有するジオールと、有機ポリイソシアネートとを反応させて得られたイソシアネート基含有ウレタンプレポリマーであることが好ましく、予め、ジイソシアネートのヌレート体における一部のイソシアネート基とメトキシポリエチレングリコールとを反応させて得られたポリイソシアネート、及び、高分子ポリオールとを反応させて得られた、イソシアネート基含有ウレタンプレポリマーであることが最も好ましい。
また、本発明のノニオン性水系ウレタン樹脂組成物は、更に、鎖延長剤及び水を含有することが好ましい。 Average composition formula (I):

However, in the above formula, n is a number of 2.6 to 10, m is 0 or 1, R is each independently a hydrogen atom, an alkyl group or a phenyl group, A is a single bond, -C (CH _{3 2} ) It represents _2- , -SO _2- , -S- or -O-.
The isocyanate group-containing urethane prepolymer having a nonionic group in the present invention preferably has a polyethylene oxide chain, and in particular, it is obtained by reacting a polymer polyol and a diol containing a polyoxyethylene group with an organic polyisocyanate. The preferred isocyanate group-containing urethane prepolymer is a polyisocyanate obtained by reacting a part of the isocyanate groups in the nurate body of diisocyanate with methoxypolyethylene glycol, and a polymer polyol. Most preferably, it is an isocyanate group-containing urethane prepolymer obtained by
The nonionic aqueous urethane resin composition of the present invention preferably further contains a chain extender and water.

  Since the nonionic water-based polyurethane resin composition of the present invention is excellent in storage stability under acidic conditions and flexibility of a coating film, it is for use in special clothing, for interiors of transportation vehicles such as automobiles, aircraft, buses and railway vehicles. , For furniture (chair, sofa, curtain, closet, etc.), other than housing, for building materials used in public facilities such as hotels, cinemas, public halls, etc., or for paints as well as electronic circuit board materials etc. Is also suitable.

The nonionic water-based polyurethane resin composition of the present invention will be described in detail below, but the present invention is not limited to these descriptions, and can be easily obtained by those skilled in the art based on the specification. It is natural that the present invention is also included in the present invention.
In the paint of the present invention, various additives usually used in paints, such as known dyes / pigments, antifoaming agents, solvents, etc. are appropriately added to the nonionic water-based polyurethane resin composition of the present invention, as necessary. It can be easily prepared.

The isocyanate group-containing urethane prepolymer having a nonionic group used in the present invention is an isocyanate group-terminated prepolymer having a nonionic group, obtained from a high molecular weight polyol and an organic polyisocyanate, and in particular having a polyethylene oxide chain preferable.

  The method of introducing the nonionic group can be appropriately selected from known methods, and for example, a method of manufacturing by replacing a part of the high molecular weight polyol with a diol containing a polyoxyethylene group, or There is a method in which a part of the isocyanate groups in the nurate body of diisocyanate and the methoxypolyethylene glycol are reacted in advance and then reacted with the high molecular weight polyol.

  The high molecular weight polyol which can be used in the present invention can be appropriately selected from those known in the art. Preferred high molecular weight polyols include, for example, polyester type polyols, polycarbonate type polyols, polyether type polyols, and dimer diols Can be mentioned.

  Specific examples of polyester-based polyols preferred for use in the present invention include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 300 to 1000, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1 Diol components such as 2,4-cyclohexanedimethanol, bisphenol A, bisphenol S, hydrogenated bisphenol A, hydroquinone and adducts of these alkylene oxides, etc. Acid, oxalic acid, adipic acid, azelaic acid, cepacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid 2,5-Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bisphenoxyethane-p, p'-dicarboxylic acid, anhydrides of dicarboxylic acid and ester-forming derivatives Polyester-based polyols obtained by dehydration condensation reaction with dicarboxylic acid components such as: polyester-based polyols obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone; and polyester-based polyols obtained by copolymerizing these . Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene isophthalate adipate diol, 3-methyl-1,5-pentane isophthalate diol, 3-methyl-1,5-pentane terephthalate diol, 1,6 -Polycondensate of hexanediol and dimer acid, etc. may be mentioned.

  Further, as a polycarbonate-based polyol preferable for use in the present invention, for example, polycarbonate obtained by the reaction of glycol such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol and the like with diphenyl carbonate, phosgene and the like Mention may be made of system polyols. Specifically, polyhexamethylene carbonate diol, 3-methyl-1,5-pentanediol carbonate diol and the like can be mentioned.

  As a polyether type polyol suitable in the present invention, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, bisphenol A, bisphenol S, hydrogenated bisphenol A, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, Low active hydrogen such as ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propanetrithiol A homopolymer obtained by addition polymerizing one or two or more of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene and the like to a compound having at least two in a usual manner And polyether-based polyols such as block copolymers and random copolymers. Specifically, homopolymers such as polytetramethylene glycol, polypropylene glycol and polyethylene glycol, block copolymers, random copolymers and the like can be mentioned.

  Moreover, as a suitable dimer diol in this invention, what has the diol obtained by reduce | restoring polymeric fatty acid as a main component is mentioned. As such polymerized fatty acids, unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, drying oil fatty acids, semi-drying oil fatty acids, lower monoalcohol esters of these fatty acids, etc. in the presence or absence of a catalyst Below, Diels-Alder type which has been subjected to a bimolecular polymerization reaction can be mentioned. Although various types of polymerized fatty acids are commercially available, representative ones are 0 to 5% by mass of a C 18 monocarboxylic acid, 70 to 98% by mass of a C 36 dimer acid, and carbon number There are some which consist of 0-30 mass% of 54 trimer acids.

  In the present invention, it is also possible to use, as the high molecular weight polyol, a polyether / ester system in which a polyether system and a polyester system are combined.

  These high molecular weight polyols may be used alone or in combination of two or more, but the average molecular weight is preferably 500 to 4,000.

  Examples of the organic polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexyl Alicyclic diisocyanates such as methane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, lysine diisocyanate, etc .; m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2 , 6-Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphene Lumethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, Aromatic diisocyanates such as xylylene diisocyanate can be mentioned. Among these organic polyisocyanates, when an aliphatic diisocyanate or an alicyclic diisocyanate is used, the resulting polyurethane resin is more likely to be non-yellowing, which is preferable. In the present invention, isophorone diisocyanate and dicyclohexylmethane diisocyanate are particularly preferable. These organic polyisocyanates can be used alone or in combination of two or more.

  Examples of the chain extender include low molecular weight polyvalent compounds such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol. Alcohol etc. can be mentioned. These chain extenders can be used alone or in combination of two or more.

  Examples of the phosphorus-based compound used in the present invention include the compounds exemplified below, but the present invention is not limited thereto.

In the present invention, it is preferable that the upper Symbol phosphorus compound having 2.0 to 15 wt% containing the resin composition of the present invention preferably has in particular 5.0 to 10.0 wt% free. In the urethane resin polymer having a nonionic group, 20 to 60% by mass of a polyethylene oxide chain is preferably contained, and particularly preferably 35 to 45% by mass is contained.
EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

In a 1-L three-necked flask, 96 g of 1,6-polycarbonate diol (average molecular weight 2000), 128 g of a diol containing polyoxyethylene group (manufactured by Perstorp, product name Ymer-N120, hydroxyl value 113), 58 g of isophorone diisocyanate 7 g of an isocyanurate form of 1,6-hexamethylene diisocyanate (product name: Duranate TLA-100, manufactured by Asahi Kasei Chemicals Corporation) and 49 g of N-ethyl-2-pyrrolidone as a solvent were uniformly mixed. The mixture was reacted at 100 ° C. for 4 hours to obtain a urethane prepolymer solution having an isocyanate group content of 2.5% by mass. The resulting urethane prepolymer solution was cooled to 60 ° C., 422 g of phosphorus-based compound (5) was added, and mixing was performed while maintaining the temperature at 60 ° C. until uniform.
Next, 500 g of the solution was transferred to an empty container prepared in advance, and while stirring, water at 40 ° C. was gradually added and mixed, and then cooled to room temperature. Furthermore, 2.1 g of ethylene diamine as a chain extender is added together with water and mixed at 25 ° C. until disappearance of the isocyanate group as measured by IR, nonvolatile content 30 mass%, viscosity 200 mPa · s / 25 ° C. pH = 6, the phosphorus content in the non-volatile content of 5 mass%, to obtain a nonionic water-based polyurethane resin composition.

In a 1-liter three-necked flask, 27 g of isocyanurate of 1,6-hexamethylene diisocyanate (Dalanate TLA-100 manufactured by Asahi Kasei Chemicals, product name Duranate TLA-100), 50 g of methoxy PEG, and 49 g of N-ethyl-2-pyrrolidone as a solvent The reaction mixture was homogeneously mixed and reacted at 100 ° C. for 4 hours to obtain a reaction solution having an isocyanate group content of 8% by mass. The resulting reaction solution is cooled, 96 g of a 1.6-polycarbonate diol (average molecular weight 2000) is added and mixed, reacted at 100 ° C. for 4 hours, and a urethane prepolymer having an isocyanate group content of 1.5% by mass. A solution was obtained. Next, the obtained urethane prepolymer solution was cooled to 60 ° C., 375 g of phosphorus compound (5) was added, and the mixture was mixed until the temperature was kept at 60 ° C. until uniform.
Subsequently, 500 g was transferred to an empty container prepared in advance, and while stirring, warm water at 40 ° C. was gradually added and mixed, and then cooling was performed to room temperature. Furthermore, 1.4 g of ethylenediamine as a chain extender is added together with water and mixed at 25 ° C. until disappearance of the isocyanate group as measured by IR, nonvolatile content 30 mass%, viscosity 200 mPa · s / 25 ° C., pH = 6, the phosphorus content in the non-volatile content of 5 mass%, to obtain a nonionic water-based polyurethane resin composition.

(Comparative example 1)
In a 1-liter three-necked flask, 101.3 g of 3-methyl-1,5-pentane terephthalate diol (average molecular weight 2000), 6.0 g of dimethylolbutanoic acid, 1.3 g of 1,4-butanediol, 0.005 g of dibutyltin dilaurate And 31.3 g of isophorone diisocyanate and 60.0 g of methyl ethyl ketone as a solvent were uniformly mixed. The reaction was carried out at 80 ° C. for 180 minutes to obtain a urethane prepolymer solution having an isocyanate group content of 2.1%. The resulting urethane prepolymer solution was cooled to 60 ° C. and phosphorus compound (5) were uniformly mixed was added to 210g, were neutralized by addition of triethylamine 4.1 g. Next, the obtained solution was gradually added to another container containing 359 g of warm water at about 40 ° C., and was emulsified and dispersed using a disper blade. After the dispersion was cooled, 20.0 g of a 30% by mass aqueous solution of isophorone diamine was added as a chain extender and allowed to react for 90 minutes. Next, the obtained polyurethane resin dispersion is subjected to solvent removal at 50 ° C. under reduced pressure, so that 33 mass% of nonvolatile matter, viscosity 200 mPa · s / 25 ° C., pH = 8, phosphorus content 0.8 in nonvolatile matter An anionic water-based polyurethane resin composition was obtained in mass%.

(Comparative example 2)
Except for not using the phosphorus compound (5), in the same manner as in Example 1, nonvolatile content was obtained nonionic aqueous resin composition of 30 wt%.

(Comparative example 3)
An anionic aqueous resin composition having a nonvolatile content of 30% by mass was obtained in the same manner as in Example 1 except that dimethylolbutanoic acid was used instead of the diol containing a polyoxyethylene group.

<Test example>
The flame retardance and stability were evaluated using the resin composition obtained by the said Example and comparative example. The evaluation method is as shown below.

<Flame retardancy>
Using a processing solution prepared by diluting the polyurethane resin aqueous dispersion obtained in the above Examples and Comparative Examples so that 15% by mass of the polyurethane resin is contained in a commercially available felt, padding processing is performed at 60% reduction rate, and then 140 ° C. And dried for 3 minutes to obtain a resin-processed cloth. About the obtained resin-processed cloth, the flame retardance was measured according to A-1 method (45 degree micro burner method) described in JISL1091. In addition, the case where the afterflame was less than 3 seconds was determined as pass.

<Stability>
An acidic aqueous solution of pH 4.0 was prepared and added to the polyurethane resin dispersion so as to be 10% by mass. The solution was then filtered using a nylon filter cloth and transferred to a covered glass bottle after mixing until uniform using a stirring blade. In the state which closed the lid | cover of the glass bottle, it left still for 1 week in a 50 degreeC thermostat. After one week, the sediment at the bottom of the solution and the presence or absence of aggregates in the solution were visually confirmed, and those without precipitate and aggregates were regarded as pass (o).

<Film flexibility>
A polyurethane resin thickened to about 10,000 to 30,000 mPa with a thickener is applied to one side of a commercially available non-woven fabric so that the thickness after drying is 0.1 mm, and dried at 120 ° C. for 1 hour The feel of the non-woven fabric was evaluated on the basis of the following criteria.
○: There is no stiffness and the texture of the non-woven fabric is not impaired.
Fair: There is a slight wrinkling but no cracking of the resin occurs.
X: Large stiffness, resin cracking occurs when bent.

＊１：難燃性は６回平均の数値

* 1: The flame resistance is an average of six times

  As apparent from the results described in Table 1 above, a resin-processed cloth processed with a treatment liquid containing the nonionic aqueous polyurethane resin composition of the present invention has sufficient flame retardancy, and the present invention It was demonstrated that the nonionic waterborne polyurethane resin composition of the present invention is excellent in stability in an acidic solution.

  The nonionic water-based polyurethane resin composition of the present invention is stable under acidic conditions and is excellent in flexibility of a coating film, and is also excellent in flame retardancy despite the use of a small amount of phosphorus compound. For special clothing, for interiors of transport vehicles such as cars, aircraft, buses and railway cars, for furniture (chair, sofa, curtains, closets, etc.), as well as for housing, public facilities such as hotels, cinemas and public halls. Since it is suitable not only for building materials to be used or for paints, but also for applications such as electronic circuit board materials, it is extremely industrially significant.

Claims (6)

An nonionic group characterized by containing at least one compound selected from an isocyanate group-containing urethane prepolymer having a nonionic group and a phosphorus-based compound represented by the following average composition formula (I): Aqueous urethane resin composition;
Average composition formula (I):

However, in the above formula, n represents a number of 2.6 to 10, m represents 0 or 1, R independently represents a hydrogen atom, an alkyl group or a phenyl group, A represents a single bond, -C (CH _{3) 2 -, - SO 2} -, - S- or an -O-. The nonionic water based urethane resin composition according to claim 1, wherein the isocyanate group-containing urethane prepolymer having a nonionic group has a polyethylene oxide chain.   Furthermore, the nonionic water based urethane resin composition described in Claim 1 or 2 which mixes a chain extender and water. The isocyanate group-containing group urethane prepolymer having a nonionic group is a polymer polyol, and an isocyanate-containing urethane prepolymer obtained by reacting a polyoxyethylene group-containing diol with an organic polyisocyanate. The nonionic water-based urethane resin composition described in any one of items 1 to 3. The isocyanate group-containing urethane prepolymer having a nonionic group is reacted in advance with a polyisocyanate obtained by reacting a part of the isocyanate group in the isocyanurate of diisocyanate with methoxypolyethylene glycol, and a polymer polyol The nonionic aqueous urethane resin composition according to any one of claims 1 to 3, which is an isocyanate group-containing urethane prepolymer obtained by   A paint comprising the nonionic aqueous urethane resin composition according to any one of claims 1 to 5.